Renewable and Sustainable Energy Reviews 75 (2017) 894–908

Contents lists available at ScienceDirect

Renewable and Sustainable Energy Reviews

journal homepage: www.elsevier.com/locate/rser

An overview of the solar thermochemical processes for hydrogen and syngas MARK
production: Reactors, and facilities
⁎
H.I. Villafán-Vidalesa, , C.A. Arancibia-Bulnesa, D. Riveros-Rosasb, H. Romero-Paredesc,
C.A. Estradaa
a
Instituto de Energías Renovables-Universidad Nacional Autónoma de México. Privada Xochicalco S/N, Col. Centro. Temixco, Morelos, Mexico
b
Instituto de Geofísica, Universidad Nacional Autónoma de México, Ciudad Universitaria, México D.F. 04510, Mexico
c
Universidad Autónoma Metropolitana-Iztapalapa. Área de Ingeniería en Recursos Energéticos, San Rafael Atlixco No. 186. Col. Vicentina, Iztapalapa,
Mexico

A R T I C L E I N F O A BS T RAC T

Keywords: Hydrogen is a promising energy carrier for transportation, domestic and industrial applications. Nowadays
Thermochemical solar processes hydrogen is consumed basically by the chemical industry, but in long term its demand is expected to grow
Solar reactors significantly due to emerging markets. Hence production of hydrogen with sustainable methods is a relevant
Solar furnace issue. This work presents a review of the different CSP- aided thermochemical processes for hydrogen and
Solar tower
syngas production. For each process, some relevant solar-tested reactor prototypes are described. In a second
Solar thermal
Concentrated solar energy
part, the developed solar furnaces for investigation of thermochemical process are also discussed. In addition,
relevant research on hydrogen or syngas production in solar tower installations is presented. Finally the current
challenges of the technology and the process for its future commercialization are also analyzed.

1. Introduction
Hydrogen is the most abundant molecule in the universe; however
on earth there is no natural source of this element. Hydrogen is found
in the entire planet in a large number of molecules, like water and fossil
fuels [1]. Nowadays, hydrogen production reaches around 300 billion
of liters per year, where the chemical industry is the main consumer of
this molecule [2]. Hydrogen is used mainly by the chemical industry for
producing fertilizers, ammonia, and for petroleum refining.
Nevertheless, its consumption is expected to increase in the next years
due to emerging markets, like the fuel-cell applications (automobile
and portable devices based on fuel-cells) [3].
Nowadays, 96% of hydrogen consumed worldwide is obtained by
processes where fossil fuels are used both as raw material and energy
source. The principal process for H2 production is the steam reforming
of natural gas, which produces 48% of the world's supply, whereas
other methods like the partial oxidation of petroleum and carbon
produce 30% and 18%, respectively. The remaining 4% of H2 produc-
tion comes from water electrolysis [4]. The main disadvantages of these
processes, which make them unviable on the long term for hydrogen
production, are the generation of important greenhouse gas emissions
and the contribution to the depletion of fossil fuels. In this context,
renewable energies, such as solar, constitute a viable option to mitigate
both drawbacks. Solar energy in particular, is one of the most abundant
renewable sources on earth, and its usage for hydrogen production
represents a virtuous combination: solar energy can be concentrated to
high levels, allowing to obtain the high temperatures required to carry
out solar thermochemical processes efficiently; on the other hand these
processes constitute an alternative route to storage solar energy in a
chemical form, helping to compensate the variability of this resource.
When solar radiation is used as the power source to produce energy
carriers such as hydrogen or synthesis gas “syngas” (which is a mixture
containing different amounts of H2 and CO), they are denominated
“solar fuels”. Solar fuels can be used to generate electricity through fuel
cells, to produce heat or mechanical work, or to obtain “Synthetic
Liquid Fuels”, by means of the Fischer-Tropsch process. This last
process is a catalytic chemical method used to convert syngas to
hydrocarbons of various molecular weights that are mainly liquids.
Depending of operating conditions (catalyst, temperature, etc.) several
hydrocarbons (from methane, to paraffin) are obtained [5].
These Synthetic Liquid Solar Fuels can be easily transported with
current technology; still hydrogen transportation needs further re-
search. The most promising liquid solar fuels are methanol, dimethyl-
ether and Fischer-Tropsch diesel. For example methanol can be used in
a mixture with unleaded gasoline (85% methanol, 15% gasoline) in a
conventional engine with minor modifications. Dimethyl-ether is a
compound that can substitute diesel, because it can be used without
any modification on internal combustion engines [6].

⁎
Corresponding author.

http://dx.doi.org/10.1016/j.rser.2016.11.070
Received 14 October 2015; Received in revised form 31 August 2016; Accepted 4 November 2016
Available online 15 November 2016
1364-0321/ © 2016 Elsevier Ltd. All rights reserved.
H.I. Villafán-Vidales et al. Renewable and Sustainable Energy Reviews 75 (2017) 894–908

Nomenclature Organization
CAESAR CAtalytically Enhanced Solar Absorption Receiver
UNAM Universidad Nacional Autónoma de México GAS Solar-driven Gas-Cooled Solar Tower
PSI Paul Scherrer Institute SOLREF Solar Steam Reforming of Methane Rich Gas for synthesis
WIS Weizmann Institute of Sciences Gas Production.
SNL Sandia National Laboratory TIT Tokio Institute of Technology
CIEMAT Centro de Investigaciones Energéticas, Medioambientales SYNPET Solar gasification of Petcoke
y Tecnológicas PDVSA Petroleos de Venezuela S.A
PROMES PRocédés, Matériaux et Energie Solaire SOLSYNCSolar Fuels for Cement Manufacturing
ETH Eidgenössische Technische Hochschule Zürich HYDROSOL Solar Hydrogen via Water Splitting in Advanced
CNRS Centre National de la Recherche Scientifique Monolithic Reactors for Future Solar Power Plants
ASTERIX Advanced Steam Reforming of Methane HoSIER Horno Solar de Alto Flujo Radiativo
CSIRO Commonwealth Scientific and Industrial Research UNISON Universidad de Sonora

Solar fuels can be produced basically by three different routes: thermolysis, thermochemical cycles, reforming, cracking, and gasifica-
electrochemical, photochemical, and thermochemical. Among these tion (Fig. 2). Water thermolysis and thermochemical cycles are
different options, the thermochemical route is a promising one for solar emission-free routes, due to the fact that they use only water or a
fuels production due to higher overall efficiencies (η∼52%) [7]. The mixture of water and CO2 and concentrated solar energy. However,
considered thermochemical reactions require high temperatures, which both processes have challenges that need to be addressed before a
are reached by using concentrated solar energy as a heat source. large-scale implementation can be accomplished. On the other hand,
The purpose of this paper is to present a review of the Concentrated the last three routes (reforming, cracking, and gasification) use fossil
Solar Power (CSP)-aided thermochemical processes for hydrogen and fuels, or a mixture of fossil fuels and water or CO2, as raw materials for
syngas production. First, the different thermochemical routes are obtaining hydrogen or syngas. (Fig. 3). The main disadvantages of
described, followed by the description of relevant solar reactors these processes are that they they contribute to the depletion of fossil
developed for carrying out each of them. Then, solar concentrating fuels and produce greenhouse gas emissions. However, these emissions
systems developed for performing research on these processes and the are considerably mitigated if concentrated solar energy is used as an
relevant pilot-scale tests realized are described. Finally, the current energy source to carry out the processes, compared to the conventional
challenges that exist to implement this technology in a commercial- heating systems.
level are discussed. Because they are not 100% clean, the routes involving fossil fuels
are seen as transition processes; it is expected that their associate costs
can be competitive with the current costs of conventional hydrogen
2. Thermochemical solar-aided hydrogen or syngas
production, but with lower environmental impacts. For instance, steam
production
reforming of methane is a well-known process that can be easily
coupled to CSP- technology [6].
The use of solar energy and its effective conversion into hydrogen
All the above thermochemical processes for solar fuels production
and syngas is possible thanks to the development of new concepts and
must be performed in devices called “solar reactors”. The design of
the creation of new facilities for the conversion of solar radiation into
these reactors is different from their conventional counterparts.
heat, with temperatures ranging from 200 to 3000 °C [4]. Some of
However, it is possible to combine concepts of traditional reactor
these techniques are subject of research, and constitute an important
engineering, with the aim of reaching a uniform heating in the reactive
technological challenge. Nowadays it is possible to obtain these two
particles, for instance, as in conventional catalytic reactors. In this case
energy carriers essentially with three different solar processes: electro-
there are two important categories depending of the distribution of the
chemical, photochemical and thermochemical.
reacting material inside the reactor. In the first category, particles are
The solar electrochemical method consists in water electrolysis for
randomly distributed, e.g. packed beds and fluidized beds. The second
hydrogen or syngas production, where the electricity needed to carry
category includes structured systems, e.g. catalytic membrane reactors,
out this process can be obtained either by means of photovoltaic panels
foams and honeycomb structures. Both reactor concepts have been
or by solar thermal power plants. The second option, solar photo-
tested in thermochemical solar processes with satisfactory results [6].
chemical method uses a part of the solar spectrum which can be
Solar reactors are classified in two groups according to the way
absorbed by a photocatalyst or sensitizer to split steam/CO2 mixtures
or water molecules to produce syngas or H2, respectively. Finally, solar
thermochemical methods use concentrated solar energy provided by
CSP systems to carry out high-temperature reactions that allow
obtaining these chemical commodities.
All of these three methods are feasible and promising alternatives
for the storage of solar energy [4], however thermochemical processes
feature more interesting thermodynamic advantages [7–9]. Fig. 1
conceptually illustrate the thermochemical solar processes, in which
solar radiation is concentrated through high concentration systems, i.e.
mirror structures that track the sun and concentrate it in one point, for
example parabolic dishes, solar furnaces or solar power tower systems.
This energy is captured in a receiver or solar reactor, where high
temperatures are obtained in order to carry out the endothermic or
exothermic reactions involved in the processes to obtain “solar fuels”.
In this manner, concentrated solar energy is stored in their chemical
bonds.
Thermochemical solar fuels production has five main routes [9]: Fig. 1. Scheme of thermochemical solar processes general performance.

895
H.I. Villafán-Vidales et al.
Fig. 2. CSP- aided thermochemical solar routes for solar hydrogen or syngas production
[8]. Reprinted (adapted) from publication Solar Energy, Vol. 78, Steinfeld and Palumbo,
Solar thermochemical production of hydrogen-a review, pages No. 12, Copyright (2005)
with permission from Elsevier.
Fig. 3. Schematic of the vortex flow solar reactor [20]. Reprinted (adapted) from
publication Int J Hydrogen Energy, Vol. 31, Z'Graggen et al., Hydrogen production by
steam-gasification of petroleum coke using concentrated solar power-III Reactor design,
testing and modeling, pages No. 14, Copyright (2006) with permission from Elsevier.
radiation is used: directly [10] and indirectly irradiated [11] reactors.
In the first category, the reactive materials are directly exposed to
concentrated solar radiation, which delivers energy more efficiently to
the reaction site. Oppositely, in the indirectly irradiated solar reactors,
reactive particles are heated through an absorbing material, that
absorbs concentrated solar energy and transfers the heat by conduc-
tion, convection and radiation to the reaction site. Another innovative
type of solar reactor is the volumetric solar reactor/receiver. This type
of reactors consists in a porous ceramic matrix, where the reactive or
catalyst is deposited. A fluid is passed through the ceramic matrix in
order to perform the reaction. This ceramic matrix is directly irradiated
with concentrated solar energy with the aim to reach the reaction
temperatures. Finally, the selection of a reactor type depends on the
specific process; e.g., in the indirectly irradiated solar reactors it is
possible to heat fluids that are transparent to solar radiation, like
methane. On the other hand, directly-irradiated solar reactors deliver
heat more efficiently to the reaction site because particles are exposed
to concentrated solar energy.
Solar reactor performance is generally described with two different
efficiency parameters: energy conversion efficiency (η) and thermal
energy conversion efficiency (ηt). The first one is defined as the fraction
of solar energy input to the reactor that is stored as chemical energy, as
a result of reactions. The second one is defined as the fraction stored as
both chemical energy and sensible heat [12].
2.1. Gasification
Gasification of coal is a reaction that has been used for more than
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Renewable and Sustainable Energy Reviews 75 (2017) 894–908
100 years. In this reaction a partial combustion of coal with steam and
oxygen is carried out in a temperature range between 800 and 1500 °C.
Here the main product is a mixture of CO and H2 (syngas) in different
proportions:
2C+1/2O2+H2O→2CO+H2(g) (1)
On the other hand, gasification of biomass is a complex process that
involves several reactions. Still, it is globally an endothermic process
that requires high temperatures.
Nowadays, gasification represents a capability of 430 Mm3 of the
world's daily production of hydrogen [4]. Thus the use of concentrated
solar energy in the gasification process has several advantages: (a)
almost 30% of CO2 emissions can be reduced [13], (b) 5–25% of
feedstock can be saved, and (c) higher yields of syngas may be obtained
per unit of biomass, because it eliminates the need to consume part of
the biomass as fuel to provide heat to the process [12].
For several years there has been an important research effort to
perform both coal and biomass gasification with concentrated solar
energy [12–28]. Several solar reactor prototypes have been developed
to carry out these processes [12,14–28].
One of the first solar prototypes was proposed in the 80's and
consisted in a directly irradiated packed bed [15], where several
reactants were used: subbituminous coal, activated carbon, coke, and
a mixture of coal and biomass with steam and CO2 as gasifying agents.
The reactor consisted in an L shaped stainless-steel cavity that
provided a simple gravity feed mechanism. The lateral walls were
insulated with firebricks of 2.5 cm thick in order to reduce heat losses.
The front of the L-shaped reactor had a window of 20 cm-diameter to
let in concentrated solar radiation. This reactor was tested in the White
Sands Solar facility (White Sands, New Mexico). The authors found an
increase in gas production when solar power input was increased, and
also that the gas composition was independent of solar power when
using steam as gasifying agent. For activated carbon they obtained
55 vol% H2, 30 vol% CO, 16 vol% CO2, 0.4 vol% CH4; and for coal and
biomass mixture, values of 50 vol% H2, 25 vol% CO, 20 vol% CO2, 7 vol
% CH4 were achieved. Energy conversion efficiency oscillated between
19–48% depending the reactive powder; e.g., activated carbon pre-
sented a maximum energy conversion efficiency of 34%.
Directly irradiated solar prototypes consisting in fluidized bed
reactors were also developed in different variants [18–23,25–28], for
instance the internally circulating fluidized bed. However all these type
of reactors have a batch reactants feeding. More recently another type
of solar reactor prototype was proposed with a continuous reactants
feeding. This reactor consisted in a 5 kW vortex-flow solar prototype,
designed to perform the solar gasification of petroleum coke from
Petróleos de Venezuela [20,21]. The reactor consists in a cylindrical
cavity-receiver with an aperture to let concentrated solar energy in. The
cavity is lined with ceramic foam, and a window in the aperture closes
the system keeping a controlled atmosphere. The window is kept clean
from particles or condensable gases using tangential gas injectors. The
coke particles are fed continuously using a particle inlet placed on top
of the reactor, in the same plane of the steam injection system in order
to obtain an immediate entrainment of particles by the steam flow.
There is another steam injection system placed in other part of the
reactor. The idea of having these injectors in different places was to
create a vortex-flow inside (Fig. 3).
With the above prototype, the authors achieved energy conversions
efficiencies between 4.8% and 8.6% and average molar flows of
0.2 mol/min H2, 0.064 mol/min CO, 0.04 mol/min CO2, and
0.007 mol/min CH4, with a syngas quality of H2:CO ~3 which,
according to the authors, is higher than the one obtained in a
conventional gasification process [20] A second experimental campaign
with this reactor used slurry feeding [21]. The slurry was a mixture of
petroleum coke particles and water. This mixture was used because this
particular kind of feeding configuration offers an easier scalability,
H.I. Villafán-Vidales et al. Renewable and Sustainable Energy Reviews 75 (2017) 894–908

45%–51, and for CO was 0.5–16% for glucose.

In general, research in solar reactors designs for gasification has
concentrated on the improvement of both directly and indirectly
irradiated horizontal reactors. Little research has been devoted the
development of vertical solar reactors, which may be due to scarcity of
solar installations with beam down optics. However beam down solar
installations offers some advantages, for example the installation of a
vertical solar reactor and accessories on the ground is much easier than
elevated horizontal reactors.
Continuous reactant feeding has also been scarcely studied, due to
the complexity of the reactor design, although some important efforts
have been carried out.
The majority of the reactor designs for solar gasification are of
laboratory or pilot scale (from 2 to 24 kW) [12]. Regarding energy
efficiencies it can be appreciated that packed bed reactors show better
results. Vortex flow reactors allow having a continuous reactant feeding
but with lower energy efficiencies, which may be due to limitations in
Fig. 4. Scheme of the double-cavity 5 kW packed-bed prototype [23]. Reprinted
(adapted) with permission from Energy & Fuels, Vol. 22, Piatkowski and Steinfeld,
area of irradiated surface (particles that are effectively irradiated). The
Solar-driven coal gasification in a thermally irradiated packed-bed reactor, pages No. 9, main drawback in vortex flow reactors is the high gas flow in order to
Copyright (2008) with permission from American Chemical Society. keep the continuous gas-particle flow, which raises costs of the process.
The majority of research efforts has been dedicated to gasification
transport, and injection of reactants. With this configuration, the of biomass, petroleum coke, and coal, while much less work has been
authors achieved energy conversion efficiencies between 0.5% and devoted to other carbonaceous materials, like industrial sludge, tire
4.7% with average molar flow rates of 0.05 mol/min H2, 0.02 mol/min scrap, or other wastes [12].
CO, 0.01 mol/min CO2 and 0.001 mol/min CH4, for a syngas quality of
H2:CO ~2.5. Another experimental campaign with this reactor proto-
2.2. Reforming
type was the solar gasification/pyrolysis of petroleum vacuum reside
(VR) [22]. The idea was to produce syngas in a mixture similar to the
The most studied materials in steam reforming of hydrocarbons are
one obtained when using petroleum coke. In this experimental
methane and natural gas, because they contain more hydrogen per
campaign the authors found energy conversion efficiencies up to 2%.
gram than other hydrocarbons [2]. In this process, methane (the
The average molar flow rates of gaseous products were 0.08 mol/min
primary component of natural gas) reacts with steam at temperatures
H2, 0.03 mol/min CO, 0.01 mol/min CO2, 0.002 mol/min CH4.
between 800–1000 °C, in the presence of a catalyst; e.g., nickel [5]. The
Negligible amounts of volatile hydrocarbons were also observed.
result of this reaction is syngas [29,30]:
Regarding the indirectly irradiated solar reactors, Piatkowski and
Steinfeld [23], designed a 5 kW packed-bed prototype. The reactor had CH4+H2O→CO(g)+3H2 (2)
two cavities separated by a SiC coated graphite plate. The lower cavity
The steam reforming of natural gas is one of the most widely used
contained the reactant particles consisting in beech charcoal, whereas
the upper cavity served as solar absorber, where the graphite plate industrial processes for the production of syngas, due to the rapid
reaction and almost complete chemical conversion achieved [2].
acted as the absorbing surface and also as radiant emitter to the lower
cavity. The idea of the double cavity design was to keep the quartz Moreover, it is nowadays the cheapest method for hydrogen produc-
tion, with a cost in the range of 2–5 USD per kilogram [30].
window clean, avoiding contact with the reactant particles (Fig. 4).
With this prototype, authors tested several carbonaceous feedstocks: In the reforming of methane it is also possible to use CO2 instead of
steam as gasifying agent [31]:
industrial and sewage sludges, scrap tire powder, fluff, South African
coal and beech charcoal, achieving energy conversion efficiencies of CH4+CO2→2CO(g)+2H2 (3)
28%, 18%, 17.3%, 15.9%, 23.3% and 29%, respectively. The gas
products contain mainly H2, CO, CH4, and CO2, with molar flow rates This reaction is performed at temperatures between 1000 and
that depend on the type of feedstock. The maximal molar flows were 1200 K in the presence of a catalyst of rhodium, palladium or nickel
0.6 mol/min H2 and 0.4 mol/min CO for industrial sludges; 0.25 mol/ [31].
min H2 and 0.15 mol/min CO for sewage sludges; 0.3 mol/min H2 and
0.15 mol/min CO for scrap tire; 0.15 mol/min H2 and 0.1 mol/min CO
for fluff; 0.3 mol/min H2 and 0.2 mol/min CO for African coal and
0.3 mol/min H2 and 0.25 mol/min CO for beech charcoal. In general
the syngas obtained in all the experiments had typical molar ratios of
H2/CO=1.5 and CO2/CO=0.2.
Another indirectly irradiated solar reactor is the one designed by
Chen et al. [24]. This reactor was designed to perform the thermal
gasification of biomass in supercritical water. The reactor consists in a
cavity receiver with a SS 316 stainless steel serpentine tubular reactor
inside (Fig. 5). This system was designed for temperatures up to 927 K
and pressures up 30 MPa. Experiments were performed on a solar
concentration system developed by the Institute of Electrical
Engineering of the Chinese Academy of Science, where the authors
Fig. 5. Schematic view of the solar reactor for the thermal gasification of biomass with
gasified glucose and corn meal with wheat stalk. The obtained molar supercritical water [24]. Reprinted (adapted) from publication Int J Hydrogen Energy,
fraction of H2 was 41.4–43.1% and for CO was 0.5–4.5% for corn meal Vol. 35, Chen et al., Hydrogen production by biomass gasification in supercritical water
wheat stalk mixture. For glucose, the molar fraction of H2 was about using concentrated solar energy: system development and proof of concept, pages No. 8,
Copyright (2010) with permission from Elsevier.

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H.I. Villafán-Vidales et al. Renewable and Sustainable Energy Reviews 75 (2017) 894–908

In the last 25 years there has been a significant amount of research conical quartz window (Fig. 7a). A compound parabolic concentrator
on the reforming of methane, natural gas and other hydrocarbons using (CPC) was placed in front of the reactor. The radiation reflected by this
concentrated solar energy [30–42]. This research has involved several concentrator entered through the window, impinging on the absorber.
institutions and laboratories, like the Paul Scherrer Institute (PSI), This absorber consisted in an alumina base with inserted tubes that
Swiss Federal Institute of Technology (ETH), Weizmann Institute of form the porcupine section. (Fig. 7b). Once inserted, the tubes were
Sciences (WIS), Sandia National Laboratory (SNL), Centro de coated with Ruthenium catalyst developed by Berman et al. [42], whose
Investigaciones Energéticas, Medioambientales y Tecnológicas process increased the catalyst´s durability and resistance to tempera-
(CIEMAT), Procédés, Matériaux et Energie Solaire (PROMES-CNRS), ture. The reactor was tested on the Solar Tower Test Facility of the
Deutches Zentrum für Luft-und Raumfahrt (DLR), Commonwealth Weizmann Institute. With this reactor prototype the authors performed
Scientific and Industrial Research Organization (CSIRO), Tokio several experimental runs in order to analyze the influence of gas
Institute of Technology (TIT), and Niigata University. The work of pressure and flow rate on the CH4 conversion. Methane conversion was
these institutions and laboratories has been focused on two main high (85%) even at high pressures (8 bars), and the results indicate that
activities: the demonstration of general concepts with concentrated the temperature within the conversion affects more than the pressure.
solar energy and the improvement of catalytic systems [6]. For methane reforming, the majority of research efforts have been
The first activity led to the design and testing of several solar dedicated to develop pilot and large-scale reactors (30–500 kW). The
reactor prototypes, which includes: 1) directly irradiated solar reactors research has tended to focus on the development of volumetric solar
based on volumetric porous receivers, 2) indirectly irradiated cavity- reactors because features better thermal and performance properties
type solar reactors based on tubular arrays, and 3) reactor/receiver than indirectly irradiated systems; nevertheless the principal disad-
with reflux of molten salts. The first two concepts have been extensively vantages in this type of reactors are linked to the absorber material.
developed [32]. This should be more resistant to thermal stress, and catalyst sintering
The first solar experiments were aimed at determining the feasi- should be reduced. So far, investigations have been confined to
bility of methane reforming using concentrated solar energy. These reforming of natural gas or high-purity CH4. Few works have investi-
experiments were performed in 1982 in a tubular solar reactor with gated the reforming of other sources of methane, like biogas [6].
Ruthenium as catalyst, and were implemented in the White Sands Regarding the gasifying agent, CO2 or steam can be chosen, and
Solar Furnace [6]. In the late 80s and beginning of the 90s the interest each option depends on final application. A mixture of both gasifying
in this solar process revived. Several laboratory prototypes were tested agents has been considered more recently as an option for methane
with both directly and indirectly irradiated configurations [6,30–42]. sources with high CO2 content, such as biogas [6].
Directly irradiated solar reactors usually use volumetric structures
composed of ceramic foams or reticulated structures. These kind of 2.3. Hydrocarbon cracking
solar reactors have been widely developed on a laboratory scale, and on
the other hand on a scale of a few hundreds of kilowatts of solar input The cracking of hydrocarbons consists in breaking up heavy
[6]. Other solar experiments have also been performed in indirect molecules into smaller ones [29]. The general reaction of this process
reactors heated with air or salts, as heat transfer medium [6]. is:
Some of the first large scale solar experiments of directly irradiated
volumetric-receiver/reactors were carried out for the reforming of CxHy→xCHy−1(g)+y/2H2 (4)
methane with CO2, within a project called “catalytically enhanced solar
Hydrocarbon cracking with concentrated solar energy has been
absorption receiver (CAESAR)” conducted by DLR and SNL [40]. The
explored basically for methane. The cracking of methane in particular
solar prototype consisted in a 100-kWth receiver with a porous ceramic
aims to produce H2 eliminating the emissions of CO2 to the environ-
foam disk inside it. This foam was coated with Rhodium 0.2 wt% as
ment. Also solid carbon is obtained as a useful byproduct of this
catalyst. Methane and CO2 flowed through the porous disk and the
process with several applications [49].
products were removed from the backside of the reactor. The disk was
The solar cracking of methane has been widely studied by several
directly irradiated with concentrated solar energy provided by a
researchers at different laboratories, among them PROMES-CNRS,
150 kW parabolic dish. The target of the project was to demonstrate
PSI, and ETH [34,43–53]. Several directly or indirectly irradiated
the technical feasibility of the solar driven process as well as the control
prototypes have been built for this reaction. In all cases the heating is
process strategy of varying the feed flow to an unsteady solar energy
input. The reactor reached efficiencies up to 85% and chemical
efficiencies peaked at 54%.
Afterwards, DLR and WIS designed and built another type of
directly irradiated solar reactor for a power solar input up to 300 kW
and pressures of 3.5 bars [31]. It consisted in a semi-spherical cavity
with a sponge-like porous ceramic inside. Two types of porous ceramic
catalytic systems were tested, one based on alpha alumina and other on
silicon carbide. Both ceramic matrices were coated with the Rh catalyst
in different proportions between 0.05 and 90 wt% (Fig. 6). The reactor
was tested on the Solar Tower Test Facility of the Weizmann Institute.
The authors found that the use of ceramic matrix structures was
suitable for solar reactors due to high solar absorption, heat transfer
and low-pressure drops. They also found some coke deposits in the
absorber system due to problems in the section were CO2 is removed
from the product gas (methanation section) in the closed-loop system.
They concluded that at operation temperatures above 800 °C there
were some degradation effects in the catalytic system, which they
attributed to specific conditions and problems with the loop system.
Fig. 6. Schematic presentation of the solar chemical reactor/receiver [31]. Reprinted
With this prototype, methane conversions above 80% were achieved. (adapted) with permission from Catalysis Today, Vol. 46, Wörner et al., CO2 reforming of
Another relevant directly irradiated solar reactor was a “porcupine methane in a solar driven volumetric receiver-reactor, pages No. 10, Copyright (1998)
reformer” [41], which consisted in a porcupine catalytic absorber and a with permission from Elsevier.

898
H.I. Villafán-Vidales et al.
Fig. 7. (a) Schematic diagram of the porcupine solar reactor and (b) absorber sections [41]. Reprinted (adapted) with permission from J Sol Energy Eng., Vol. 133, Rubin and Karni,
Carbon Dioxide reforming of methane in directly irradiated solar reactor with porcupine absorber, pages No. 8, Copyright (2011) with permission in process from American Society of
Mechanical Engineering.
Fig. 8. Scheme of the 5 kW particle flow cavity-reactor [48]. Reprinted (adapted) with
permission from Int J Hydrogen Energy, Vol. 34, Magg et al., Solar methane cracking of
methane in a particle-flow reactor for the co-production of hydrogen and carbon, pages
No. 10, Copyright (2009) with permission from Elsevier.
carried out by infrared radiation, because methane absorbs in this
spectral range [43]. In the case of directly irradiated prototypes, these
involve particulate material, e.g. carbon black, which absorbs solar
radiation and transfers heat to the fluid (CH4) [46,47]. Some of the
relevant solar prototypes are described below.
ETH and PSI designed a 5 kWt solar prototype that consisted in a
particle-flow cavity-type reactor [48]. Carbon black particles were used
as radiant absorbers and nucleation sites for the heterogeneous
reaction. The heterogeneous flow (formed by methane and carbon
black particles) entered both radially and axially, forming a laminar
axial flow through the cavity (Fig. 8). This flow was directly irradiated
by concentrated solar energy provided by the PSI high-flux solar
furnace. The authors performed a parametric investigation on several
parameters such as, the carbon particle volume fraction, gas inlet flow
rate, methane inlet molar fraction, and incoming radiation flux. With
this reactor prototype, authors reached methane conversions and
hydrogen yields above 95%. The average energy conversion efficiency
achieved was 9.1% for maximum incoming solar power of 4.87 kW.
Results indicated that the chemical conversion increases when the
particle volume fraction or the incoming radiative flux are increased,
because of improved radiation absorption by the carbon particles. The
gas inlet flow rate presented a weak influence, whereas an increase of
the methane molar fraction reduced the reaction extent due to the
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Renewable and Sustainable Energy Reviews 75 (2017) 894–908
Fig. 9. (A) Scheme of the solar experimental reactor and (B) geometry of the graphite
nozzles tested in [43]. Reprinted (adapted) with permission from Int J Hydrogen Energy,
Vol. 30, Abanades and Flamant. Production of hydrogen by thermal methane splitting in
a nozzle-type laboratory-scale solar reactor, pages No. 11, Copyright (2005) with
permission from Elsevier.
higher specific heat of methane.
Abanades et al. [43–47,49–51] designed two different types of solar
reactors: directly and indirectly irradiated. In particular, the authors
designed a laboratory-scale directly irradiated prototype that consisted
in a graphite nozzle where a mixture of methane and Argon is flowed
(Fig. 9a). In this work, authors tested several geometries of the nozzle
target [43] and they found that the geometry has an important effect in
the chemical conversion and thermochemical efficiency (Fig. 9b).
Methane conversions ranged from 11.6% to 23.4% and H2 mole
fractions of 0.016–0.091 were achieved. Thermochemical efficiencies
varied from 0.5% to 1.8%.
One example of an indirectly irradiated solar reactor was a
prototype of 10 kW that consisted in a cubic cavity with four tubular
sections placed inside the cavity where the cracking of methane was
performed [49] (Fig. 10a). Every section consisted of two concentric
graphite tubes with independent reactive feeding, in order to increase
the residence time. Authors tested several configurations of the internal
graphite tube (Fig. 10b). With this reactor configuration, the authors
reached maximal methane conversions of 98% and H2 yield in the
range of 80–95%, obtaining carbon nanotubes as a byproduct with high
H.I. Villafán-Vidales et al. Renewable and Sustainable Energy Reviews 75 (2017) 894–908

Fig. 10. (a) Schematic view of the 10 kW solar reactor and (b) Cross section view of the tube configurations tested [49]. Reprinted (adapted) with permission from Int J Hydrogen
Energy, Vol. 34, Rodat et al., Solar methane cracking of methane in a particle-flow reactor for the co-production of hydrogen and carbon, pages No. 10, Copyright (2009) with permission
from Elsevier.

commercial value (for a cavity wall temperature of 1770 K, a residence respectively.

time of 32 ms and a CH4 mole fraction of 10%) [49,51]. During
experimentation authors found that two parameters impact the che- 2.5. Thermochemical cycles
mical conversion: the residence time and the temperature.
As in gasification, research has tended to focus on the deployment The drawbacks of the direct water thermolysis prompted the study
of solar reactors for the thermal decomposition of pure methane, of the water-splitting thermochemical cycles. The analysis of these
paying much less attention to the use of other sources of methane, such cycles began in the early 60s with a project called Energy Depot, which
as biogas. aimed at producing fuels from materials such as earth, air and water.
Regarding directly irradiated solar reactors featuring continuous This attracted the attention of the scientific community and, in the late
particulate material as radiant absorbers; the main disadvantage is 60s, the search for novel cycles suitable for efficient hydrogen produc-
observed in the window, which must be protected against particle tion was initiated [59]. The first proposed cycles consisted in several
deposition. The use of indirectly irradiated reactors avoids this steps, but some of these processes proved to be too complicated for
problem, but comes with its own drawbacks, like the deposition of practical solar applications [13].
carbon particles inside the reaction tubes, which may cause blocking. The simplest cycles, the two-step cycles require higher tempera-
tures, but are much more efficient. The first one was proposed by
2.4. Thermolysis Nakamura, in 1977, based in the reduction of Fe3O4 to FeO [60]. In
such processes, high temperatures are used, but these temperatures are
Water thermolysis consists in the dissociation of water molecules quite lower than those required for water thermolysis; moreover the
into hydrogen and oxygen: problem of hydrogen and oxygen separation is avoided because the
production of both occurs in different steps [8], i.e:
H2O↔H2+1/2O2 (5)
MOox→MOred+(1/2)O2 (6)
Despite its conceptual simplicity, this process is not easily achieved
because the bonding between oxygen and hydrogen is one of the most
energetic in nature. This reaction needs temperatures above 2900 K to MOred+H2O→MOox+H2 (7)
reach a reasonable degree of dissociation (around 35%) [54]. Such high Where MO stands for a metal oxide. The first step of this cycle (Eq. (6))
temperature level is one of the major disadvantages for this process,
which has limited its development. At these temperatures there are
several problems with the reactor materials. Another drawback is that
gaseous products must be separated immediately after the dissociation
reaction to prevent recombination. If effective separation is not
performed, the reaction could end up in an explosive mixture [9].
In the 70s and early 80s water dissociation experiments were
performed using solar energy [55–57]. More recently the study of the
thermolysis of water has not received much attention since the problem
of the availability of materials that withstand such high temperatures
persists; however some tests were more recently made in a 1 kWth
solar furnace located in Montreal, Canada [58]. For these tests a
horizontal solar reactor was designed. This reactor consisted in a
cylindrical cavity with walls made of zirconia or alumina and insulated
with porous ceramic material. The feed water was introduced down in
the reactor´s wall in order to evaporate it before entering the cavity
(Fig. 11). Quenching steam was also introduced in the front of the
reactor, near the reaction zone through four perpendicular jets. With Fig. 11. Schematic of the solar reactor for the thermolysis [58]. Reprinted (adapted)
this reactor configuration the authors achieved efficiencies of 1.1% and with permission from Int J Hydrogen Energy, Vol. 29, Baykara, Experimental solar water
H2 mole fractions of 0.03 and 0.00012 at 2500 K and 1500 K, thermolysis, pages No. 10, Copyright (2004) with permission from Elsevier.

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H.I. Villafán-Vidales et al.
is an endothermic reaction that requires temperatures above 1000 K.
In this reaction, a metal oxide is reduced at high temperatures,
producing oxygen and a reduced metal oxide. The second step (Eq.
(7)), consists in an exothermic reaction (hydrolysis) at temperatures
below 1000 K. In this step, the reduced oxide is used to perform water
dissociation, and the products obtained are hydrogen and the original
oxide. The net result of both reactions is water splitting.
An important difference that thermochemical cycles have in com-
parison to other thermochemical processes, such as gasification or
reforming, is that here the starting compounds are regenerated and
used again; hence the term "cycle".
One of the main advantages of these cycles is that pure hydrogen is
obtained, without the contaminants, such as carbon monoxide, en-
countered while producing H2 from fossil fuels. This pure hydrogen can
be used directly in PEM (Proton Exchange Membrane) fuel cells.
Thermochemical cycles can also be used to dissociate CO2 into CO,
i.e.
MOox→MOred+(1/2)O2 (8)
MOred+CO2→MOox+CO (9)
With these reactions, CO2 is revalorized into a CO as an alternative
to the CO2 sequestration. Additionally, it is also possible to obtain
syngas by mixing CO2 and H2O, i.e.
MOox→MOred+(1/2)O2 (10)
MOred+H2O+CO2→MOox+CO+H2 (11)
The resulting syngas can be used to produce synthetic liquid fuels
through the Fischer-Tropsh reaction [5]:
nCO+2nH2→CnH2 n+nH2O (12)
Many thermochemical cycles have been experimentally tested with
concentrated solar energy to date. Some of the redox pairs that have
been tested are: Fe3O4/FeO [60–66], TiO2/TiOx [67], Mn3O4/MnO
[62,66,68], Co3O4/CoO [66], ZnO/Zn [69–81] SnO2/SnO
[78,79,82,83] CuO/Cu2O [84] and CeO2/Ce2O3 [85–88]. These cycles
are classified in the literature as “volatile” and “non-volatile” cycles,
according to whether the reduced metal oxide continues in a solid-
phase during the entire process or not [89]. Therefore the design of the
solar reactor depends on type of cycle. “Volatile” redox pairs exhibit a
solid to gas phase transition of the reduced metal oxide; hence the
reactor design must contemplate this phase change [89]. For example,
in the ZnO cycle the Zn product is in gas phase, thus the reactor must
consider the quenching of the products, in order to recuperate Zn and
to avoid possible recombination of Zn with O2. On the other hand, in
“non-volatile” cycles the reduced oxide remains in the solid phase
during the whole process [89], avoiding the need of a quenching
system. Thus the physicochemical characteristics of the redox material,
such as porosity, particle size, specific surface area, became important
[89], specially for the second step (Eqs. (7), (9) and (11)).
To study solar fuels production via thermochemical cycles, re-
searchers have designed many solar reactors, from simple designs like
fixed beds to more complicated configurations such as volumetric
receivers or vortex-flow reactors. The goal is to achieve higher
thermochemical efficiencies and a continuous feeding of the reagent.
Some of the most relevant solar reactors are described below.
Chambon et al. [79], designed a moving front solar reactor to
perform the solar dissociation of compressed ZnO and SnO2 powders,
in order to obtain Zn or SnO. The 1 kW solar reactor consisted in a
vertical cylindrical cavity. In the bottom of the reactor, the reactant in
the form of an oxide rod was pushed upward with a piston, in order to
achieve a continuous reactant injection. With this reactor configura-
tion, authors could determine the kinetics of the ZnO dissociation
reaction. The prototype allowed obtaining 1 gr of powder with
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Renewable and Sustainable Energy Reviews 75 (2017) 894–908
significant amount of reduced species (average mol fraction of 20%
and 36% for ZnO and SnO2, respectively) in less than half an hour. An
average thermochemical efficiency in the range 1–3% was achieved.
In 2008, Driver et al. [91] designed a new reactor concept that
consisted in a counter rotating ring receiver/reactor/recuperator
(CR5). The authors proved with this reactor the recovery of sensible
heat during cyclic operation. This reactor has two rotating fixed beds
with ferrite reactant material moving in opposite directions.
Concentrated solar radiation impinges the front of the rotating rings.
The intermediary rings are used to recover the sensible heat and the
final part is used to perform the hydrolysis reaction (Fig. 12). One of
the advantages of this prototype is that the reactant is supported, thus
it is compatible with concentration systems with variable orientations
relative to gravity, like for example parabolic dishes. The reactor was
designed to reach a thermal efficiency of 32.2%, a reaction extent of
35%, and a hydrogen production rate of 0.0412 mol/s with an incident
solar power of 15 kW.
The CR5 was also used for the study of syngas production with ceria
oxides, in a project called “Sunshine to Petrol” [92,93], whose objective
is to show a solar thermochemical pathway for the efficient production
of liquid fuels from CO2 and H2O feedstock. In these tests a peak
efficiency of 1.7% and peak CO production rate of 100 cm3/min were
achieved.
Another innovate solar reactor concept consists in a volumetric
porous reactor, which was also proposed for solar reforming. This type
of reactor use either ceramic foams or regular porous structures, like
honeycombs. The reactor has no moving parts and the porous structure
is coated with the redox pair material. When steam or a mixture of CO2
and steam passes trough the porous media, the metal oxide, which is in
a reduced state, splits water by retaining its oxygen (Fig. 13). To
complete the cycle, the metal oxide is reduced again at high tempera-
ture by solar heating, while passing an inert gas through the porous
media to extract the produced oxygen [87,88,94–96].
One of the reactors consisted in a honeycomb structure made of re-
crystallized and siliconized Silicon Carbide (Fig. 13a) [95]. The receiver
was insulated and fixed in the stainless-steel cylindrical housing. The
focus of the concentration system (DLR solar furnace) was located on
the front of the honeycomb. The honeycomb was coated with iron-
oxide-based redox materials synthetizied with three different routes, as
well as the component oxides Mn3O4, NiO, ZnO and Fe2O3. All the
materials were tested for hydrogen production at the temperatures
ranging from 750 to 1100 °C. The total hydrogen yield and mol
conversion obtained during the experiment depends on redox material
and they are in the range of 4–812 mol H2/g solid and 0.75–80%,
Fig. 12. Scheme of the CR5 solar reactor [91]. Reprinted (adapted) with permission
from J Sol Energy Eng., Vol. 130, Diver et al., Solar thermochemical water- splitting
ferrite- cycle heat engines, pages No. 8, Copyright (2008) with permission in process
from American Society of Mechanical Engineering.
H.I. Villafán-Vidales et al.
Fig. 13. (a) Scheme of the two-chamber “Honeycomb” reactor [95]. Reprinted (adapted)
with permission from Int J Hydrogen Energy, Vol. 34, Roeb et al., Operational strategy of
a two-step thermochemical process for solar hydrogen production, pages No. 8,
Copyright (2009) with permission from Elsevier. (b) Scheme of the reticulated porous
media solar reactor [87]. Reprinted with permission from Energy & Fuels, Vol. 26,
Furler et al., Solar thermochemical CO2 splitting utilizing a reticulated porous ceria redoc
system, page No. 7052, Copyright 2012 American Chemical Society.
respectively [94–96].
Another concept of volumetric solar reactor was used for the study
of the production of syngas with the CeO2/CeO2−x thermochemical
cycle [87,88]. The solar reactor was a cylindrical cavity with a 4 cm
diameter aperture for entrance of the radiation provided by the High
Flux Solar simulator of the Swiss Federal Institute of Technology in
Zurich (ETH). The novelty of this reactor is that the reticulated porous
ceramic foam is made of pure CeO2, which is directly reduced to a non-
stoichiometric state. This porous foam was contained within the cavity
as a cylinder composed of 20 mm-thick, 60 mm- i.d., 100 mm-o.d rings
and a single disk of 20 mm-thick, 100 mm-o.d, which is placed at the
bottom (Fig. 13b). Based on experimental data, an average thermal
efficiency of 0.09% was obtained for ten consecutive H2O/CO2 feeding
cycles. The average O2 release during the reduction step was 2.89 ml
per gram of CeO2 and fuel production was 5.88 ml per gram with a
H2:CO molar ratio controlled in a range from 0.25 to 2.34 A 10–20 kW
novel beam-down gravity feed solar reactor was proposed to accom-
plish the first step of the ZnO/Zn thermochemical cycle [97]. The
reactor consisted in a inverted conical-shape cavity composed of fifteen
trapezoidal Al2O3 tiles supported by layers of porous ceramic insula-
tion. Near the aperture there were 15 hopper assemblies that allow
feeding ZnO powder in the range of 0.05–3g/s in batch or semi-
continuous mode. With this configuration, the reactant powder forms a
moving reactive bed that is directly irradiated with concentrated solar
energy. The ZnO product vapor exits the reactor through a centrally
located exit tube. Un-reacted or partially reacted solids exit annularly
around exit tube. During experimentation radiation power input was
kept constant at 3.5 kW. Authors varied reactant feed rates from 0.74
to 4.21g/s, totaling 8–15 kg per experiment. The reactor was also used
to perform carbothermal reduction of ZnO [97]. In this case a mixture
of ZnO powder and charcoal particles was continuously fed. Peak solar
thermochemical energy conversion efficiency of 12.4%, Zn flow rates of
0.10 mol/min, reactant conversion of 14%, and high quality zinc
product (average 75% puriry) were achieved.
It is important to point out that in the case of thermochemical
cycles temperatures required to reach full conversion in the endother-
mic step are high, typically between 1100 and 2300 K [6]. Thus, most
studies in this area have focused in the development of directly
irradiated reactors. The use of carbonaceous materials, such as coke,
coal, biomass, methane, etc., as reducing agents, is an attractive option
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Renewable and Sustainable Energy Reviews 75 (2017) 894–908
for lowering the reduction temperature. The solar driven carbothermal
and methano-thermal reduction proceeds as follows [97]:
MOox+δC→MOred+(2δ−1)CO+(1−δ)CO2 (13)
MOox+δCH4→MOred+δ(CO+2H2) (14)
In this case, lower temperatures allow designing simpler reactors
with no moving parts, and directly irradiated reactors are preferred,
which could easily scale up to a pilot-scale. An example is the 5–10 kW
double cavity solar reactor (Fig. 4) designed by Piatkowski and
Steinfeld [23]. This reactor prototype was tested for the gasification
of carbonaceous materials, as well as for the carbothermic reduction of
ZnO with several sources of carbon, such as coke, coal, activated
charcoal, beech charcoal, petroleum coke, bituminous coal and lamp
black. In these last experiments, authors identified the critical para-
meters for designing the 300 kW pilot scale solar reactor within the
ZOLZINC project [89,90,98], which aimed to produce 50 kg of ZnO per
hour, through carbothermic reduction of ZnO. For this process,
thermal efficiencies between 12% and 20% and Zn mol of 0.79–1.54
were achieved.
3. Solar furnaces
A solar furnace is an optical system consisting of a heliostat with
automatic sun tracking, which reflects solar radiation to a stationary
concentrating mirror (Fig. 14). This mirror can be a single parabola or
a group of spherical facets. In solar furnaces it is easy to install and
carefully control different experiments because the focal zone of the
concentrator mirror is stationary, as the sun tracking is carried out by
the heliostat instead of the concentrator. The power level in the focal
zone of the solar furnace is adjusted by using a shutter, which works
like a Venetian blind, and is located between the heliostat and the
concentrator.
Solar furnaces are systems designed to provide highly concentrated
solar radiation in very controlled experimental environments. These
devices are ideal to carry out research and development in high
temperature solar driven processes, like materials testing and synth-
esis, and solar chemistry. For instance, CSP technologies require the
development of receiver materials able of withstanding thermal cycling
under highly concentrated solar radiation. The development of these
materials requires environments suitable for laboratory experimenta-
tion and prototype testing in similar high flux conditions. Solar
furnaces provide clean working environments, free of contaminants
such as dust, chemical or electrical effects; the intensity of the radiation
can be accurately controlled and quickly modified. Of course, a solar
furnace has limitations inherent at its operating conditions [99]; for
instance, it should be located in areas of few clouds, experimental tests
Fig. 14. Schematic of a solar furnace illustrating its main components.
H.I. Villafán-Vidales et al.
can be performed only intermittently and usually only small samples
can be treated. Moreover, the cost of a solar furnace of medium size
(2.5–5 cm solar spot) is moderately high due to their optical quality
requirements. This cost rapidly increases with the spot size becoming
extremely high for large capacity solar furnaces with spot sizes above
10 cm.
The technology of solar furnaces has its beginnings in the second
half of the 50's decade. From the beginning they were developed with
the goal to be scientific research instruments [99]. The first solar
furnace was developed by the Arizona State College in the United
States, in 1956 [100], and the second one was developed by the
Governmental Industrial Research Institute in Japan [101]. The
temperatures achieved for these furnaces were, respectively, 1855 °C
(Zirconia melting point), and approximately 2300 °C. Early research on
solar furnaces was intended to determine the effect of high tempera-
tures on various materials properties exposed to highly concentrated
radiative fluxes [102,103]. Nowadays solar furnaces cover a wide range
of applications [102–105]:
• Processing and manufacturing of advanced materials
• Determination of thermo-physical properties under concentrated
radiation, including thermal expansion coefficient, thermal conduc-
tivity and diffusivity, specific heat, mechanical properties, and
spectral emittance and emissivity.
• Determination of the operation limits and fatigue limits of metallic,
ceramic and refractory materials
• Accelerated aging of materials by UV radiation.
• Development of receivers for CSP technology.
• Testing of CPV cells.
• Thermochemical processes to produce solar fuels.
• Simulation of thermal effects in the presence of highly concentrated
radiative flux.
• Destruction of toxic materials: industrial, organic, medical waste,
etc.
• Atmospheric effects in the solar form and in the performance of
concentration systems
A difficult problem from the beginning has been the measurement
of high temperatures in the presence of concentrated solar radiation
[106], as well as the measurements of the concentrated flux distribu-
tion itself [107]. Nowadays, digital imaging techniques are used [107–
109], together with calorimetric techniques.
Besides the early facilities, several other solar furnaces have been
developed along the years, which are described below:
3.1. The CNRS solar furnace
Located in the south of France, in the Pyrenees near the town of
Font-Romeu-Odeillo, it stands one of the largest solar furnaces in the
world. It consists of 1830 m2 of reflective surface on a parabolic
structure, with a focal length of 18 m. The concentrator was built in
the façade of a 40 m high research building, and it is illuminated by a
group of 63 heliostats, with 2835 m2 total reflective area. The CNRS
solar furnace focuses 1 MW to a spot about 80 cm in diameter, and
achieves a mean concentration ratio of 10000 suns and a black body
equivalent temperature of 3800 °C [110]. Due to its large dimensions,
the furnace does not have a shutter in front of the concentrator, instead
a gate is located on the wall of the receiver room.
In the same facility as the 1 MW CNRS solar furnace there are
eleven small to medium size furnaces built with parabolic mirrors of
different sizes and orientations. In vertical axis position there are four
parabolas of 2 m diameter, four parabolas of 1.5 m diameter, and one
parabola with 6 kW of solar thermal power. A pair of 2 m diameter
parabolas operates with horizontal axis position.
A solar furnace very similar to the one above was built by the
Academy of Sciences of the Republic of Uzbekistan [111], with the
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same dimensions and power.
3.2. The PSI solar furnace
PSI's High-Flux Solar Furnace is located in the north of
Switzerland, near Zurich. The solar furnace consists of a parabolic
concentrator capable of delivering 40 kW of thermal power and a flat
heliostat on the focal axis of the concentrator. It achieves a peak solar
concentration ratio of 5000 suns. The average flux concentration is
approximately 3500 suns, with a solar spot of 6 cm of diameter. The
concentrated solar flux is measured with a CCD camera over a cooled
Lambertian flat target, and the power input is regulated with a
Venetian-blind shutter.
3.3. The NREL solar furnace
The NREL high flux solar furnace is located near the city of Denver,
Colorado, USA. The device consists of a sun-tracking heliostat with an
area of 32 m2, and a concentrator with 25 hexagonal curved mirrors.
The heliostat and the focal point are off-axis to avoid shadowing on the
mirrors. The solar furnace can reach up to 1,800 °C with a mean
concentration ration of 2500 suns in a spot diameter of 10 cm.
3.4. The DLR solar furnace
This solar furnace is located to the south of Cologne, Germany.
DLR's Solar Furnace consists of an array of 159 hexagonal spherical
mirrors which concentrate radiation from the sun into an opening in
the laboratory building´s wall. The focal point is off axis with the
mirror system, avoiding shadowing on the mirrors. The total area of the
concentrator is 42 m2 with an average focal length of 7.3 m. Each
individual mirror has an edge length of 32 cm. The concentrator
mirrors are coated with aluminum on the front side and are protected
by a vapor-deposited silicon oxide layer. The heliostat is a flat mirror
with a total area of 57 m2. The front side of the mirrors is coated with
titanium oxide to guarantee the reflection of solar radiation´s UV
spectrum. The DLR solar furnace reaches temperatures above 2000 °C
with a mean solar flux of 5200 suns.
3.5. The CIEMAT solar furnace
The biggest solar furnace at Plataforma Solar de Almería (in the
Tabernas desert, in the south of Spain) consists of a sun-tracking
heliostat and a solar concentrator with 81 curved mirrors. The shape of
the mirrors concentrator is square shaped approximately 1 m2. The
focal length for the optical system is 7.45 m. The total solar thermal
power of the solar furnace is 69 kW within a spot diameter of 25 cm,
and a peak concentration ratio of 3000 suns.
3.6. The Valparaiso University solar furnace
This device is located in the state of Florida, USA. This solar furnace
consists in a 306 hexagonal shaped mirrors array. The total solar
thermal power is 10 kW with a mean solar flux of 3000 suns over a
6 cm diameter spot. The solar furnace reaches temperatures over
1650 °C.
3.7. The IER-UNAM Solar furnace
A high Flux Radiative Solar Furnace (HoSIER, by its acronym in
Spanish) has been developed at the Instituto de Energías Renovables,
Universidad Nacional Autónoma de México (IER-UNAM), located in
Temixco, Mexico [112,113].
The HoSIER consists of a concentrator, a heliostat, a shutter with
vertical blinds, and a working table with accurate three-dimensional
movement. The concentrator is composed of 409 spherical hexagonal
H.I. Villafán-Vidales et al.
mirrors with spherical curvature and 20 cm apothem. The mirrors are
grouped into five concentric focal lengths from 3.75 to 4.75 m. The
heliostat consists of 30 flat mirrors, and it has a reflectance area of
81 m2.
The optical evaluation of the HoSIER has shown a very small global
optical error of about 2 mrad, in excellent agreement with theoretical
modeling [113]. The peak flux in the focal zone is 18,000 suns, with
and an average flux of 5,700 suns in 7.2 cm-diameter zone, where more
than 95% of the radiative flux is concentrated [112]. Temperatures
above 3400 K have been demonstrated through the melting of tungsten
in an inert atmosphere [113].
4. Solar tower facilities
Solar tower technology (also known as central receiver technology)
was originally conceived for electricity generation [114]; however, solar
towers are seen today as the most suitable CSP technology to carry out
solar thermochemical processes on industrial scale. A solar tower plant
consists of a field of independent tracking mirrors, known as heliostats,
which concentrate solar radiation into a receiver located on top of the
tower. This geometry is conceived in order to maximize the optical
efficiency of the system on a yearly basis.
When used for electricity generation, the solar tower receiver is
usually a heat exchanger where a thermal fluid (water/steam, molten
salts, air) is heated. The collected heat can be either used to power a
Rankine or a Brayton cycle or stored for nighttime generation. A solar
reactor that carries out thermochemical processes can replace this kind
of receiver if the goal is solar fuels production. A second plant design
concept locates the reactor on the ground instead of on the tower. This
is the “beam-down” concept, where a secondary hyperbolic mirror,
located up in the tower, redirects the radiation concentrated by
heliostats to the reactor´s aperture on ground level. From an optical
point of view this is equivalent to the Cassegrain configuration used in
telescopes.
Beam-down systems were first proposed by Rabl [115] for electrical
power production. Segal and Epstein [116] proposed its utilization in
solar hydrogen plants. They latter proposed a method for a substantial
decrease in the ground´s secondary concentrator cluster dimensions,
to get a more cost-effective design of beam-down plants [117]. The
beam-down configuration has some advantages in terms of reducing
the complexity and weight of the equipment installed on the tower, but
on the other hand it has drawbacks, which have been pointed out by
Vant-Hull [118].
Different theoretical analyses have been published for the coupling
of solar towers to thermochemical reactors. Some of them are
summarized here.
The coupling of a large-scale solar tubular reformer with a beam-
down tower plant was theoretically analyzed by Segal and Epstein
[119]. The proposed reformer comprises 7 units; each unit has tubular
reactors filled with catalyst. These tubes are heated by concentrated
solar radiation entering at the top of the reformer, which is similar to
the top-fired type conventional reformers. In the study, it was demon-
strated that with a tube diameter of 70–160 mm and a heated length of
10–12 m, conversions above 92% could be achieved. The authors
mention that the synthesis gas obtained by this technology can be
used for the production of methanol. This gas can feed a methanol
plant with a capacity of 36,000 t/year, while operating during sunny
hours. If the system is hybridized, the process can feed a plant having a
capacity of about 140,000 t/year. In the work, they also discuss the
coupling of this system to 100 MW combined cycle power generation
unit.
Kolb et al. [120] analyzed the coupling of a high-temperature
(1000 °C) power tower with a sulfuric acid hybrid thermochemical
cycle, including a solid particle receiver and a particle thermal energy
storage system. The design of the solar receiver is simple and similar to
the receiver used at Solar Two, and it uses sand as a heat transfer
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media. The cycle is “hybrid” because it produces hydrogen using a
combination of thermal input and an electrolyer. The proposed plant
would have a large nitrate salt energy storage system that would allow
to achieve > 70% annual capacity factor. Authors predict that this plant
would produce ≈14 million kg of hydrogen per year at levelized cost of
$5.1/kg.
Methodological aspects of the design of solar thermal chemical
processes to be implemented in solar towers were discussed by
Martinek et al. [121]. In particular, they consider ZnO and NiFe2O4
water splitting cycles. The ZnO and NiFe2O4 processes were scaled and
simulated in AspenPlus to produce 3.65×107 kg of hydrogen annually
(annual average of 100,000 kg H2/day) and operate 365 days per year.
In the analysis the solar reduction of both oxides proceeds during
daylight hours, whereas the oxidation step operates continuously. It
was assumed that the thermal reductions occur at 1800 °C (for ZnO
cycle) and at 1400 °C (for NiFe2O4). They also implement an alternate
definition for the efficiency of the process, which has strong implica-
tions on the process and the solar field design.
Pitz-Paal et al. [122] discussed the optimization of the heliostat
layout in a solar plant, considering two different termochemical
processes: thermal reduction of zinc oxide and coal gasification. The
layout is optimized for maximum annual´s energy conversion effi-
ciency, from solar to chemical. Simulation results indicated that the
system is best designed for a solar flux density of 4600 suns, operating
at 1900 K, for zinc oxide reduction, and of 2500 suns at 1300 K for coal
gasification. The solar-to-chemical energy conversion efficiencies were
estimated to be 30% and 40% for zinc oxide reduction and coal
gasification, respectively.
Säck et al. [123] described a model for the operation of a metal
oxide cycle power plant, using a ferrite coated on a monolithic
honeycomb absorber. This refers to the special plant and process
design where two solar receiver/reactors are alternated between the
reduction and oxidation steps of the cycle. This requires a special
control of the heliostats, alternating between the two receivers and
taking into account weather conditions, like DNI fluctuation, clouds
and wind speed. Also, the fast switching after completion of half-cycles
and the shutdown must be controlled.
Several works have been published regarding experimental imple-
mentations of solar termochemical processes in actual solar towers
[31,124–131]. These are discussed below along with the different
facilities where tests were performed.
4.1. Weizmann Institute of Science Solar Tower
The Solar Tower of WIS started operations in 1988. It consists of 64
heliostats with a 7 m×8 m area. They reflect solar radiation to a 54 m
high five level experimental tower. Each level of the tower can house
several experiments. Until very recently, this was the only Solar Tower
facility in the world located on an academic institution, and thus solely
dedicated to scientific work.
In 1995 the beam-down concept was implemented for the first time
in this facility, using a hyperbolic 75 m2 reflector attached to the tower,
45 m above ground level. With this arrangement, 1 MW of concen-
trated solar radiation can be focused onto a ground target.
The WIS has the longest record on solar fuels production research
at solar tower installations. Different fuel production methods have
been investigated, including: hydrocarbon reforming, methane decom-
position, solar thermal-electrochemical dissociation of water at high
temperatures, biomass gasification, and metal oxide cycles. Among the
activities carried out:
CO2 reforming of methane was investigated [31] at WIS solar
tower. Two catalytic materials were developed for the volumetric
receiver, based on Ru supported over ceramic a-Al2O3 and SiC foam
structures. The system operated at 300 kW, reaching temperatures up
to 860 °C, and achieving methane conversions over 80%.
An innovative 400 kWt solar reactor for syngas and hydrogen
H.I. Villafán-Vidales et al.
production was tested in the solar platform of the WIS within the
SOLREF (Solar Steam Reforming of Methane Rich Gas for synthesis
Gas Production) project carried out between 2004 and 2010 [125]. An
advanced and more compact volumetric reformed was designed. The
reactor was able to operate at 950 °C and 15 bar, resulting in higher
methane conversions. A new catalytic system was also implemented,
which allows to operate with a broad range of feed gas compositions,
such as biogas, and contaminated natural gas [6].
A 300 kW solar reactor for the carbothermic reduction of ZnO was
experimentally demonstrated in the beam-down of WIS as part of the
SOLZINC project [126], carried out between 2001 and 2005. The
reactor was an indirectly irradiated double cavity, where the upper part
acted as absorber, and the second as reaction chamber. The reactor
operated in the range 1300–1500 K with a conversion efficiency of
30%. It was possible to produce 50 kg/h of 95%-purity Zn.
4.2. CESA-1 and SSPS/CRS towers at Plataforma Solar de Almería
The Plataforma Solar de Almería, belonging to CIEMAT, has two
solar tower facilities SPSS-CRS (Small Solar Power System – Central
Receiver System) and CESA-1. The first one consists of a 91 heliostats
north field and a 43 m tower. Three different platforms can be used as
test rigs. The nominal heliostat field thermal power is 2.5 MW. In the
past, this facility had been used for testing small solar receivers in the
range of 200–350 kW thermal power. Nowadays, the solar tower
accommodates test beds for hydrogen production projects [127]. The
CESA-1 tower has a thermal capacity of 5 MW and a 80 m-high
concrete tower with four test levels. It also has a north heliostat field.
The Advanced Steam Reforming of Methane (ASTERIX) project
was performed in the late 1980s and early 1990s by DLR and CIEMAT
[6]. A steam reformer was driven by hot air produced in the system
known as Solar-driven Gas-Cooled Solar Tower (GAS). Up to 0.36 kg/s
of hot air at 1000 °C and 9 bar were produced. A tubular 170 kW
reformer with a fixed-bed catalyst was used in the production of
industrial quality syngas achieving chemical conversions in the range of
68–93%.
Within the HYDROSOL II project [95–124], a 100 kW pilot plant
for two-step solar thermo-chemical water-splitting was implemented at
PSA. A volumetric honeycomb ceramic reactor coated with iron oxides
was used. With this prototype, significant concentrations of hydrogen
were produced with a conversion steam up to 30%. In the first three
half-cycles, 35 g of H2 were produced. Authors mention that if the
experiment was extended all over the day, is possible to obtain 500 g of
hydrogen. A double reactor concept makes possible to run both the
reduction and oxidation steps simultaneously to produce hydrogen in a
quasi-continuous mode. This double operation is accomplished by
alternating high temperature reduction and low temperature oxidation
steps between both reaction chambers. This is achieved by a control
that shifts heliostats dynamically from one chamber to the other as
required in order to regulate temperature [124].
Modeling of this two-step hydrogen production plant has been
carried out by de la Calle A et al. [128]. The dynamic model includes
both the solar field and the reactor and it was calibrated and validated
with experimental data. The numerical predictions showed good
agreement with measurement data.
The SYNPET project (2003–2012) was performed by CIEMAT and
ETH along with Petróleos de Venezuela (PDVSA). Experimental tests
performed at the SSPS tower [129] included gasification of petroleum
coke and solids derived from crude oil in a 300 kWt solar reactor,
obtaining up to 30% H2.
The SOLSYN, project was performed by PSI, ETH and the Holcim
cement company. A 150 kW reactor was developed to produce syngas
thorough gasification of carbonaceous compounds, such as industrial
sludge, fluff, tire chips, dried sewage sludge, low-rank coal, and sugar
cane bagasse. The idea was to burn the syngas to obtain heat to drive
the cement production processes [98]. Nine different carbonaceous
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Renewable and Sustainable Energy Reviews 75 (2017) 894–908
materials were successfully converted into solar-upgraded high-quality
synthesis gas, with thermal efficiencies between 22% and 35%.
4.3. CSIRO Solar Towers 1 and 2
The CSIRO Solar Tower 1 was developed in 2005, at the Energy
Centre in Newcastle, Australia. Designed with a high ground coverage
heliostat concept [130,131], it has a 804-m2 reflector area and consists
of 179 heliostats, 1.84-m wide and 2.44-m high each. It is capable of
delivering 500 kW into a 0.8×0.8-m2 square aperture. Different solar
fuels research projects have been performed in this solar tower, as
described below.
More recently the Solar Tower 2 was developed, consisting of a 450
heliostats field for a total 4000-m2 area, and a 30-m high tower.
The steam reforming of natural gas was demonstrated in 2006 on
the 500 kW CSIRO solar tower 1 [31]. Solar reformers able to achieve
high methane conversions at low temperatures (823–973 K) were
developed with a considerable reduction in the cost of producing
hydrogen by this route. Such solar reformers consisted in indirectly
irradiated reactors where a catalyst is packed in between the inner and
outer tubes. The production of H2 via steam reforming of natural was
demonstrated at temperatures and pressures up to 850 °C and 20 bar.
For a demonstration facility the reactor was designed for up to 1000 h
of operation using a high temperature stainless steel. CSIRO also
designed a much larger, hexagonal-shape, dual-coil reformer capable of
processing natural gas at 850 °C and 1 bar pressure [6].
4.4. UNAM/UNISON Solar tower
The development of this facility started in 2010, 10-km from the
city of Hermosillo, in the Sonoran desert, by Universidad de Sonora
(UNISON) and Universidad Nacional Autónoma de México (UNAM).
The field design includes 82 heliostats forming a 36-m2 area in a north
field configuration, for a total nominal power of 2 MW thermal. There
are currently 35 units like these already installed, the rest of them will
be installed in subsequent phases of the project. Heliostats have canted
facets for producing concentration. The tower is 36-m high, supporting
with a 8×7 m2 Lambertian target, and a testing platform with 4×4-m2
aperture.
No experimentation on solar termochemical processes has been
carried out yet in this facility, still that´s one of the main objectives for
its development. In conjunction with IER-UNAM solar furnace, these
facilities provide the necessary infrastructure for the future develop-
ment and scale up of processes and reactors.
Thermochemical solar hydrogen production in solar towers has
been scarcely studied. As can be seen from the above discussion,
research on these solar installations has emphasized of reforming of
natural gas with steam or CO2, because this is a well know commercial
process, whose production cost through solar energy can became
competitive in the short term. Nevertheless the cost of this technology
depends strongly on natural gas prices [4].
5. Challenges
All thermochemical processes described above have been tested
experimentally, and there is certainty about their technical feasibility.
However, they have not reached yet a stage of maturity that allows their
implementation on a large scale. The commercial deployment of this
technology requires solving challenges in basic research and technology
development; some of them are described below:
a) New materials for solar reactor design
The design materials constitute an important part of solar
reactors. The insulation and the inner surfaces of the reactor are
usually built out of ceramic fibers and high temperature ceramics,
respectively e.g. high purity alumina, zirconia, SiC, fibers alumina,
H.I. Villafán-Vidales et al.
among others. The inner materials must withstand very high
temperatures, in some cases above 2000 K. But in addition to high
temperatures, they must be able to tolerate large thermal gradients
and rapid temperature increases (up to 1000 K/s, as in the CNRS
solar furnace). Both factors cause significant thermal stresses,
which can fracture the material.
Another important element is the solar reactor window. The
window is generally made with quartz, because this material is not
only transparent to solar radiation (0.3–2.5 µm), but also resists
high temperatures (about 1200 °C). On the other hand, quartz has a
very poor resistance to temperature gradients, therefore windows
need to be keep cold and free of any deposit or encrusted material
that could damage them by opacity or reacting with it. An
alternative option to quartz windows is the borosilicate glass
window. This material can withstands lower temperatures than
quartz ( < 600 °C), still requires care to avoid deposits that may
cause fractures, but it is much cheaper.
The use of indirectly irradiated solar reactors avoids the use of
windows, but heat transfer in them is less efficient because higher
involved thermal resistances. In this case the absorbing material
must be selected carefully because it must withstand high tempera-
tures, it must be inert to the chemical reaction, have good thermal
conductivity, high absorptance in the solar spectrum, and resistance
to thermal shocks.
Further research in all these different materials is necessary.
b) Design and scaling-up of solar reactors
The design and scaling-up of solar reactors is a complex task
that requires a multidisciplinary approach. In such reactors com-
bined heat transfer mechanisms (conduction, convection and
radiation) coexist with mass transfer, optical phenomena and
chemical reactions. The modeling of such systems requires the
development or use of highly specialized software.
c) Developing of new catalyst and redox materials.
One of the most important challenges for the commercial
deployment of solar thermochemical processes is the limited
availability of materials that resist high temperatures. An option
to circumvent this is to develop new catalysts that allow decreasing
reaction temperatures, and improving the chemical conversion of
the processes. In the case of redox pairs to perform water dissocia-
tion through thermochemical cycles, further work in the recovery of
reduced materials and separating gases mixtures is required, if
volatile cycles are employed. On the other hand, when non-volatile
cycles are used, it is necessary to avoid melting or vaporization that
may produce losses of the redox material. Melting also produces big
particles that need to be grinded to fine powder for further
utilization, making whole process more complicated [89]. More
research in novel redox pairs is required to study experimentally
and theoretically their viability.
d) Continuous operation and process control
The continuous operation of thermochemical process represents
an important challenge. The continuous feeding of reactants and
removing of products, as well as the separation and cooling of these
products is an unsolved problem. On the other hand, the energy
source of these processes is a variable source. Therefore control
systems must be capable to absorb these variations and keep the
operation of the reactors. In this perspective, it is necessary to
develop new reactor concepts that allow the continuous feeding of
reactants and the removing of products while keeping a constant
chemical conversion.
e) Thermophysical properties of the materials at high temperatures.
The determination of the thermophysical properties of the
reactants and reactor construction materials is a relevant issue, in
order to carry out a good reactor design or scaling-up. Nowadays
this issue has been scarcely researched. Further work need to be
done in this issue so as to determine the variation of mechanical,
thermal and optical properties in several conditions of temperature
906
Renewable and Sustainable Energy Reviews 75 (2017) 894–908
and pressures for different materials. Regarding the kinetic para-
meters, many empirical correlations obtained at low temperatures
are used, whose valid at high temperatures cannot be ensured
[132]. Development of methodologies for determination of all of
these parameters at high temperatures is required, especially for
reactions that have been scarcely analyzed.
f) Cost reduction in concentration systems
As in the generation of electricity with solar power systems, the
reduction of cost in the concentration system is a fundamental issue in
order to reach the commercial viability of thermochemical process.
Most of the thermochemical processes are suitable for implementation
in central receiver systems. In this type of plants, almost half of the cost
is related with the heliostat field. Therefore it is necessary to impulse
the research and development of more efficient thermochemical
process, as well as the components of the heliostat field in order to
reduce costs.
In conclusion, the future commercialization of these processes
depends on the long-term industrial financiation in order to have a
long-term demonstration plant that helps to identify the relevant issues
in large-scale technology [6].
Acknowledgements
The authors acknowledge the financial support received from the
Sector Fund CONACYT-SENER-ENERGY-SUSTAINABILITY, through
the Mexican Center for Innovation in Solar Energy (CeMIE-Sol), Grant
207450, within Strategic Project No.10 COSOLpi “Solar Fuels and
Industrial Processes”. Also, support from PAPIIT-DGAPA-UNAM
program, grant IA101115, is acknowledged.
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